N-trifluoromethylated sulphenamides and process for the production thereof



United States Patent 3,236,842 N-'IRIFLUOROMETHYLATED SULPHENAMIDES AND PROCESS FOR THE PRODUCTION THEREOF Erich Klauke, Cologne-Flittard, and Engelbert Kiihle,

Cologne-Stammheim, Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Filed July 24, 1962, Ser. No. 212,114 Claims priority, application Germany, July 26, 1961, F 34,531 9 Claims. (Cl. 260247.1)

The present invention relates to and has as its objects new and useful insecticidal, acaricidal and fungicidal compounds. More specifically this invention relates to N-trifluoromethylated sulphenamides of the general formula Ar-SR as Well as to a process for the production of such compounds.

In the above formula Ar represents an optionally substituted aromatic radical, while R is 'an optionally substituted aliphatic or aromatic radical, a heterocyclic radical or a secondary optionally cyclic amino group, and R can further stand for a halogen atom or a radical XS, whereby X is chlorine or bromine, the second halogen atom then being capable of reaction with a second molecule of N-trifluoromethyl aryl amine.

Finally this invention is concerned with improvements in insecticidal, fungicidal and acaricidal preparations and more particularly to improved insecticides, acaricides and fungicides as well as to methods of protecting organic material especially plants subject to attack by insects and fungi.

In accordance with the present invention it has been found that the N-trifluoromethylated sulphenamides of the above mentioned general formula are distinguished by outstanding insecticidal, fungicidal and acaricidal properties combined with a good plant tolerance and a high initial and long lasting activity. The compounds are therefore particularly suitable as pest control agents, especially for plant-protecting and controlling the growth of fungi.

The novel inventive compounds can be prepared by reaction of sulphenic acid halides of the general formula with N-trifluoromethyl aryl amines of the formula Ar-NH preferably in the presence of acid-binding agents. The reaction according to the present invention may be represented by the following general scheme:

This scheme is only given for the purpose of illustrating the invention and is not intended to limit it in any Way.

3,236,842 Patented F eb. 22, 1966 In the aforementioned formulae the symbols Ar, X and R have the significance as given above.

The N-trifluoromethyl aryl amines necessary as starting materials for the inventive process can readily be produced from aromatic isocyanide dichlorides and fluoric acid according to K. A. Petrov: Z. obsc. Chem. 29, 2169 (1959). Suitable compounds are e.g. N-trifluoromethyl aniline, chlorinated and/ or nitrated N-trifluoromethyl anilines or -toluidines, N-trifluoromethyl naphthyl amines and 1,4-bis-N-trifiuoromethyl phenylene diamines.

As sulphenic acid halides to be reacted according to the invention there can be used for example methanesulphenic acid bromide, fluorodichloro-methane sulphenic acid chloride, perchloromethyl mercaptan, bromochlorofluoroand dibromofluoromethane sulphenic acid bromide, benzene-sulphenic acid chloride, 4-nitrobenzene-sulphenic acid chloride, pentachloro-benzene-sulphenic acid chloride, benzthiazolyl-Z-sulphenic acid chloride, morpholine sulphenic acid bromide, trimethyl-sulphamido-sulphenic acid chloride, monosulphur dichloride, and disulphur dichloride.

The reaction according to the present invention is conducted expediently at room temperature or slightly elevated temperatures preferably in the presence of an acidbinding agent and in an inert organic solvent.

As solvents there may be considered optionally halogenated aliphatic and aromatic hydrocarbons e.g. chloroform, carbon tetrachloride, benzene, chlorobenzene, xylol, toluol, dioxane and the like and as acid-binding agents alkali-hydroxides, -alcoholates, -carbouates or tertiary amines have been proved. In some cases, however, it is also possible to carry out the inventive reaction in an aqueous alkaline medium if the stability of the correspond.- ing sulphenic acid halide is suflicient.

As already mentioned above the new N-trifluoromethylated sulphenamides are valuable pesticides and possess especially an outstanding insecticidal, acaricidal and fungicidal action. They are therefore employed as plant protection agents, mainly as insecticides and fungicides. Furthermore the inventive compounds serve as intermediate products for further organic syntheses.

As an example for the special utility the inventive compounds of the following formulae ol-Qn-s con have been tested against spider mites, caterpillars and mustard flies (compounds I and HI) and against mosquito larvae (compound II).

Aqueous dilutions of these compounds have been prepared by mixing the active iugredients with the same amounts of dimethyl fonnamide as an auxiliary solvent adding thereto 20% by weight referred to active ingredient of a commercial emulsifier consisting of a benzyl hydroxy polyglycol ether containing about 10 to 15 glycol ethers,

termined after 24 hours. The following results have been obtained:

and diluting this premixture at last with water to the 5 desired concentration indicated in the following para- Compound aqueous concen- Killing graphs: traumas? 532.3?)

The tests have been carried out as follows. (a) Against spider mites: Bean plants (Phaseolus vul- (I) 0 02 100 garis) of about 15 inches height are sprayed drip Wet (III) 0 2 100 with solutions as prepared above and in a concentration as shown below. The bean plants have been infested heavily with the two-spotted spider (species Tetranychus telarius) Evaluation has been carried out after 24 hours, (d) Against mosquito larvae f the type Aedes aegypti; 48 hours and 8 days- The followmg results have been About larvae were brought into diluted aqueous emulobtamed: sions prepared as described above. Counting of the dead pests occurred after 24 hours. The following results have been obtained:

Compound aqueous ooncen- Killing tration (in percent active rate (in ingredient/water) percent) Co po d q e s co e fl q tration (in percent active rate (in ingredient/water) percent) (I) 0.2 100 (III) 0.2 100 25 0 0001 70 *(b) Against caterpillars of the type diamondback moth The f ll i examples are given f the purpose f (Plutella maculipennis): White cabbage has been sprayed illustrating the invention; drip wet with aqueous emulsions as prepared above in a concentration as shown below. Caterpillars (10 each) have been placed on the sprayed leaves of the white cab- Exam le 1 bage. The living status has been determined after 24 p and 48 hours. The following results have been obtained: 0 -Q-N-SOFC1z JFa O d Kmn 19.6 g. of 4-chloro-N-trifiuoromethyl aniline (B.P. 74

1'11 11 o g g f iiggf g g g to 75 C./10 mm. Hg) are dlssolved in 100 ml. of beningredient/water) percent) zene with additlon of 10.1 g. of triethylamme and subsequently the mixture is treated dropwise at room temperar) o 2 100 ture, with cooling, with 17 g. of fluorodichloromethane- (In) 0 2 100 sulphenic acid chloride. The reaction mixture is shaken out with water, the benzene layer dried overnight with sodium sulphate, concentrated in vacuum and the residue distilled. 27 g. of dichlorofluoromethane-N-(trifluoromethyl) N (4 chlorophenyl) sulphenamide of B.P. (c) Against mustard flies: About 50 flies (Drosophila 116-123 C./11 mm. Hg are obtained in this way. Catermelanogaster) are placed under covered petri dishes in pillars are completely destroyed by 0.2% solutions, muswhich, drip wet filter papers have been placed Which are tard flies (Drosophila melanogaster) even by 0.02% sprayed with insecticidal solutions of concentrations as solutions of the compound. In an analogous manner the shown below. The living status of the flies has been defollowing compounds may be produced:

Biological activity Structure Physical properties Aqueous eon- (B.P. in C.) centration in Killing rate Application againstpercent active (percent) ingredient/ water Caterpillars 0.2 Cl-N-SCOl 138-148/11mm. Hg {Mustard flies 0.02 100 I Spider mites 0. 2 100 CFa C t D'll 0.2 100 01 Q 1 S013 012 -135 10 mm. Hg f Q02 m0 CFs p O t '11 0.2 100 C12 Olly M u igr d iii es 0.2 100 Biological activity Structure Physical properties Aqueous con- (B.P. in C.) centration in Killing rate Application againstpercent active (percent) ingredient] water Mustard flies 0.02 100 N S C F {Spider mites 0. 2 100 H30 0 filYISCF c1? 115-130/0.15 mm. Hg Mosquito larvae 8: 33

O 0 Fa N02 1ITS OH 01.0 013 Oily NSC 013 dn Cl O1-NSC F 012 105-109 0.15 mm. Hg

N02 C1-I]-ISC F 01, Oily OzN-QlTT-SC 013 do C F3 OHs-NSCFB1-O1 .....r1

0 F3 Ol-1?SOFBrOI do C1 oi-Nscrmcl -fln JFa 01 Ger-so F 012 105-110/10 mm. Hg

I C Fe 0 F3 Cl III-S 0 C13 Oil? F F-N N IITSCFC12 N 0 F3 F Example 2 of benzene and the resulting solution is treated dropwise 0 at 20 to 30 c. with 10.1 g. of triethylamine.

19.6 g. of 4-chloro-N-trifluoromethyl aniline and 19.0 g.

Subsequently the triethylammonium hydrochloride is filtered OE With suction, the filtrate is concentrated and 35 g. 4-nitrophenyl N (trifluoromethyl) N (4-chlorophenyl)-sulphenamide in the form of an undistillable darkcoloured oil are obtained in this way. Spider mites are killed to 100% by 0.2% solutions of the compound. The following compounds result by Working in an analogous manner:

Biological activity Structure Physical properties Aqueous concentration in Application againstpercent active Killing rate iugredient/ water Spider Mites 0. 2 100 OIQNS Oily {Caterpillars 0. 2 100 l Mustard flies 0. 2 100 C F3 l OF; I O1 NO:

Cl V

Example 3 01 01 e Fa J1 Fa 0 F3 C Fa 98 g. of 4-chlorophenyl-N-trifluoromethyl aniline are dissolved in 500 ml. benzene with addition of 50.5 g. of triethyl-amine and the mixture is treated dropwise at room temperature with cooling, with 33.4 g. of disulphur dichloride. After stirring for'some time, the reaction solution is shaken out with water and the benzene layer concentrated in vacuum, after drying over sodium sulphate. There remain 85 g. of the compound of the above formula as an undistillable oil. 7

In the same Way there may be obtained the following compounds:

OFa CFa (BF: lFa

OzN-

I v l GFa CFa Fa Example 4 on on OFa CF1 We claim:

1. The compound having the formula Cl-Q-ITL-SOF 012 OFa CFs

4. The compound having the formula 5. The compound having the formula GPQIf-S o r on 01- --lTI-SOCI3 CFz 7. A compound having the formula NSR (R2011 Fa wherein R is a member selected from the group consisting of morpholino and piperidino; R is halo; R is halo; and n is a whole number of 0-1; n being defined as 1 when R is piperidino and defined as 0 when R is morpholino.

8. The compound having the formula NS-N O CFs 9. A compound having the formula RlTTS-O-X CFa X wherein R is a member selected from the group consisting of a chlorophenyl, nitrophenyl and chloro-nitro phenyl; and X is a member selected from the group consisting of chloro, fiuoro, at least two of the X groups being chloro.

References Cited by the Examiner UNITED STATES PATENTS 2,474,237 6/1949 Edy 260551 2,476,655 7/1949 Fox et al 260511 XR 2,553,770 5/1951 Kittleson 260551 XR 2,844,628 7/ 1958 Kuhle et a1. 260-551 2,867,658 1/1959 Frick 260-551 2,962,417 11/1960 Harris 16730 OTHER REFERENCES Reid: Organic Chemistry of Bivalent Sulfur, vol. 11, pages 296-7, Chemical Publishing Co., N.Y. (1960).

Stevens: Tetrahedron Letters, No. 17, pages 16 to -18 (1959).

Stevens: J. Org. Chem., vol. 26, pages 3451 to 3457 (September 1961).

WALTER A. MODANCE, Primary Examiner.

JOHN D. RANDOLPH, Examiner. 

7. A COMPOUND HAVING THE FORMULA
 9. A COMPOUND HAVING THE FORMULA 